Molecular absorption and emission

Page 1: Introduction to Spectroscopic Methods

  • Overview of molecular absorption and emission.

Page 2: Index

  • Molecular absorption

  • Applications of molecular absorption

  • UV-Vis spectrophotometers

  • Luminescence

    • Fluorescence

    • Spectrofluorometer

    • Phosphorescence

  • Applications of luminescence

Page 3: Electromagnetic Radiation Absorption

  • Compounds absorb electromagnetic radiation and generate a spectrum.

  • Different areas of absorption based on nature: IR, UV, Visible.

  • Provides qualitative or quantitative information.

  • Beer’s Law: relationship between absorbance and intensity of light.

    • Transmittance (T) defined as T = P/P0.

    • Absorbance (A) defined as A = - log T = - log (P/P0).

    • Changes in intensity depend on molar absorptivity (ε), optical path length (b), and concentration (c).

    • Beer’s Law equation: A = ε b c, where A is a function of wavelength (λ).

Page 4: Deviations from Beer’s Law

  • Validity at low concentrations only; relates absorbance (A) to concentration (C).

  • Types of deviations:

    • Intrinsic (from sample properties)

    • Instrumental (from instruments)

    • Chemical (from chemical processes)

    • Analyst errors (from handling samples)

  • ε (molar absorptivity) is influenced by the refractive index.

Page 5: Instrumental Deviations

  • Factors affecting instrument performance:

    • Electric current fluctuations.

    • Radiation source instability.

    • Nonlinear detector response.

    • Non-monochromatic radiation.

    • Parasitic radiation and its influence.

    • Reading errors in data collection.

Page 6: Chemical Deviations

  • Factors affecting chemical balance:

    • Acid-base balance (buffers needed).

    • Solvent effects (bathochromic/ipsochromic shifts due to solvent dielectric constant).

    • Temperature influence.

    • Impurities and their interaction with chromophores and functional groups.

Page 7: Analyst-related Deviations

  • Importance of proper sample handling:

    • Cleaning of sample cells (glass or quartz).

    • Measurement conditions (clean samples, no bubbles).

    • Consistency required between sample and blank measurements.

Page 8: Index

  • Reiterates topics in molecular absorption and luminescence applications.

Page 9: Applications of Molecular Absorption

  • Various applications in analyzing organic molecules.

  • Comparison of colorimetry (visible) and spectrophotometry (UV-Vis, IR).

  • Derivatization needed for inorganic compound analysis.

  • Electronic transitions in absorption spectra (types of transitions).

Page 10: Index

  • List of topics in molecular absorption and spectrophotometry.

Page 11: Single-beam Spectrophotometer

  • Description: Links to video demonstration.

  • Components include:

    • Light sources (hydrogen/deuterium, tungsten)

    • Materials for UV and visible light conditions.

Page 12: Double-beam Spectrophotometer

  • Functionality of one detector for alternating measurements.

  • More accurate results through comparative measurements.

Page 13: UV-Vis Spectrophotometers Components

  • Components include cell, monochromator, detector, and sample compartment.

Page 14: Index

  • Summary of topics covered in the document.

Page 15: Photoluminescence and Chemiluminescence

  • Types of luminescence explained:

    • Photoluminescence (fluorescence and phosphorescence).

    • Chemiluminescence (from chemical reactions).

  • Key features:

    • High sensitivity, wide concentration range, selective.

    • Easier at lower temperatures.

    • Limitations in applications.

Page 16: Luminescence Energy Diagrams

  • Electron configuration states:

    • Singlet and triplet states.

  • Energy level diagrams showing deactivation pathways of excited states.

Page 17: Index

  • Listing topics relevant to the document’s content.

Page 18: Fluorescence Intensity Formula

  • Fluorescence intensity F related to concentration:

    • F = K P0 c (P0: incident beam power, K: constant).

    • Notable sensitivity and low interference.

Page 19: Wavelength Dependence in Quinine

  • Different excitation wavelengths impacting emission wavelength.

  • Internal changes affecting emission spectra.

Page 20: Mirror-Image Rule and Franck-Condon Factors

  • Absorption and emission spectra examples (for anthracene).

  • Description of vibrational energy levels.

Page 21: Index

  • Overview of molecular absorption and applications.

Page 22: Analytical Method Development

  • Considerations for excitation and emission wavelengths.

  • Use of fluorimetric reagents for inorganic compound analysis.

Page 23: Index

  • Topics reiterated in molecular absorption and luminescence.

Page 24: Phosphorescence Durations

  • Differences in fluorescence and phosphorescence durations.

  • Instruments requiring discrimination methods.

Page 25: Index

  • Listing of molecular absorption and applications.

Page 26: Applications Overview

  • Focus on miniaturization and detection methods.

Page 27: Measurement Modes - Photometric

  • Measurement of absorbance/transmittance at specific or multiple wavelengths.

  • Applications in quantification and signal comparison.

Page 28: Spectrophotometric Measurement Mode

  • Collects full spectra over a wavelength range.

  • Applications in characterization and monitoring sample evolutions.

Page 29: Quantitative Analysis

  • Highly utilized methods with limits of detection.

  • Fast and precise methodologies.

  • Equation stating total absorbance as a sum of individual contributions.

Page 30: Quantitative Analysis Techniques

  • Use as indicators for titrations in some methods.

Page 31: Quantitative Analysis Requirements

  • Conditions for detecting non-absorbing compounds.

  • Requirements for specific reactions and sample dilution.

Page 32: Qualitative Analysis Techniques

  • Focus on complex formation and balance constants determination.

  • UV-Vis is useful for identifying certain functional groups.

  • Techniques for detecting impurities.

Page 33: Kinetic Analysis

  • Analysis focusing on product formation and compound degradation.

Page 34: Other Modes of Measurement

  • Considerations regard temperature in measurements.

Page 35: Analysis Parameters

  • Description of analysis parameters affecting results and measurements.

Page 36-39: Laboratory Equipment Types

  • Discussion of molecular absorption and fluorescence spectroscopy equipment.

  • Details on specific devices and types of samples analyzed (liquid, solid).

Page 40-53: HPLC Detectors and Applications

  • Overview on HPLC detectors and their functioning.

  • Detailed descriptions of how various detectors measure absorbance and intensity.

  • Applications in both laboratory set-ups and portable instruments.